JP6804047B2 - Triazine ring-containing polymer and a film-forming composition containing the same - Google Patents

Description

The present invention relates to a triazine ring-containing polymer and a film-forming composition containing the same.

In recent years, we have developed electronic devices such as liquid crystal displays, organic electroluminescence (EL) displays, touch panels, optical semiconductor (LED) elements, solid-state imaging devices, organic thin-film solar cells, dye-sensitized solar cells, and organic thin film transistors (TFTs). At this time, high-performance polymer materials have come to be required.
Specific properties required include 1) heat resistance, 2) transparency, 3) high refractive index, 4) high solubility, 5) low volume shrinkage, 6) high temperature and high humidity resistance, and 7) high film hardness. And so on.
In view of this point, the present inventors have found that a polymer containing a repeating unit having a triazine ring and an aromatic ring has a high refractive index, and the polymer alone has high heat resistance, high transparency, high refractive index, and high solubility. It has already been found that low volume shrinkage can be achieved and that it is suitable as a film-forming composition for producing an electronic device (Patent Document 1).

By the way, for spacers, insulating films, protective films, etc. in liquid crystal display elements, it is common to prepare a thin film by a coating method using a composition in which a high-polarity material is dissolved in an organic solvent. Depending on the type of solvent, it may not be possible to use a highly polar solvent. In particular, in a transparent conductive film using a metal nanowire that has been widely used recently, the binder of the metal nanowire is dissolved by the highly polar solvent. There was a case.
Further, after coating the film-forming composition containing a high-refractive-index polymer using a coating device, a low-polarity solvent or the like may be used as a line cleaning solvent for the device, and a polymer having low solubility in such a solvent may be used. In some cases, there was a problem that the line was clogged.

International Publication No. 2010/128661

The present invention has been made in view of the above circumstances, and can form a thin film having a high refractive index and excellent transparency, and can be dissolved in various organic solvents such as a low-polarity solvent, a hydrophobic solvent, and a low boiling point solvent. An object of the present invention is to provide a triazine ring-containing polymer having excellent properties and a film-forming composition containing the same.

As a result of diligent studies to achieve the above object, the present inventors have a triazine ring terminal, and at least a part of the triazine ring terminal is sealed with a fluorine atom-containing arylamino group. We have found that by using a polymer, a thin film having a high refractive index and excellent transparency can be formed, and a triazine ring-containing polymer having excellent solubility in various organic solvents can be obtained, and the present invention has been completed.

｛式中、ＲおよびＲ′は、互いに独立して、水素原子、アルキル基、アルコキシ基、アリール基、またはアラルキル基を表し、
Ａｒは、式（２）〜（１３）で示される群から選ばれる少なくとも１種を表す。

〔式中、Ｒ¹〜Ｒ⁹²は、互いに独立して、水素原子、ハロゲン原子、カルボキシル基、スルホ基、炭素数１〜１０の分岐構造を有していてもよいアルキル基、または炭素数１〜１０の分岐構造を有していてもよいアルコキシ基を表し、
Ｒ⁹³およびＲ⁹⁴は、互いに独立して、水素原子または炭素数１〜１０の分岐構造を有していてもよいアルキル基を表し、
Ｗ¹およびＷ²は、互いに独立して、単結合、ＣＲ⁹⁵Ｒ⁹⁶（Ｒ⁹⁵およびＲ⁹⁶は、互いに独立して、水素原子または炭素数１〜１０の分岐構造を有していてもよいアルキル基（ただし、これらは一緒になって環を形成していてもよい。）を表す。）、Ｃ＝Ｏ、Ｏ、Ｓ、ＳＯ、ＳＯ₂、またはＮＲ⁹⁷（Ｒ⁹⁷は、水素原子または炭素数１〜１０の分岐構造を有していてもよいアルキル基を表す。）を表し、
Ｘ¹およびＸ²は、互いに独立して、単結合、炭素数１〜１０の分岐構造を有していてもよいアルキレン基、または式（１４）

（式中、Ｒ⁹⁸〜Ｒ¹⁰¹は、互いに独立して、水素原子、ハロゲン原子、カルボキシル基、スルホ基、炭素数１〜１０の分岐構造を有していてもよいアルキル基、または炭素数１〜１０の分岐構造を有していてもよいアルコキシ基を表し、
Ｙ¹およびＹ²は、互いに独立して、単結合または炭素数１〜１０の分岐構造を有していてもよいアルキレン基を表す。）で示される基を表す。〕
２． 前記Ｒ¹〜Ｒ⁹²およびＲ⁹⁸〜Ｒ¹⁰¹が、水素原子である１のトリアジン環含有重合体、
３． 前記フッ素原子含有アリールアミノ基が、式（１５）で示される１または２のトリアジン環含有重合体、

（式中、Ｒ¹⁰²は、フッ素原子または炭素数１〜１０のフルオロアルキル基を表す。）
４． 前記フッ素原子含有アリールアミノ基が、式（１６）で示される３のトリアジン環含有重合体、

（式中、Ｒ¹⁰²は、前記と同じ意味を表す。）
５． 前記Ｒ¹⁰²が、炭素数１〜１０のパーフルオロアルキル基である３または４のトリアジン環含有重合体、
６． 前記Ａｒが、式（１７）で示される１〜５のいずれかのトリアジン環含有重合体、

７． １〜６のいずれかのトリアジン環含有重合体と有機溶媒とを含む膜形成用組成物、
８． 前記有機溶媒が、グリコールエステル系溶媒、ケトン系溶媒、およびエステル系溶媒から選ばれる少なくとも１種である７の膜形成用組成物、
９． さらに架橋剤を含む７または８の膜形成用組成物、
１０． 前記架橋剤が、多官能（メタ）アクリル化合物である９の膜形成用組成物、
１１． ７〜１０のいずれかの膜形成用組成物から得られる薄膜、
１２． 基材と、この基材上に形成された１１の薄膜とを備える電子デバイス、
１３． 基材と、この基材上に形成された１１の薄膜とを備える光学部材
を提供する。That is, the present invention
1. 1. It contains a repeating unit structure represented by the following formula (1), has at least one triazine ring terminal, and at least a part of the triazine ring terminal is sealed with a fluorine atom-containing arylamino group. Triazine ring-containing polymer,

{In the formula, R and R'represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group independently of each other.
Ar represents at least one selected from the group represented by the formulas (2) to (13).

[In the formula, R ^{1 to} R ⁹² are independent of each other and may have a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, a branched structure having 1 to 10 carbon atoms, or an alkyl group having 1 carbon atom. Represents an alkoxy group which may have a branched structure of 10 to 10.
R ⁹³ and R ⁹⁴ represent an alkyl group which may have a hydrogen atom or a branched structure having 1 to 10 carbon atoms independently of each other.
W ¹ and W ² are independent of each other and have a single bond, CR ⁹⁵ R ⁹⁶ (R ⁹⁵ and R ⁹⁶ may have a hydrogen atom or a branched structure having 1 to 10 carbon atoms independently of each other. Represents an alkyl group (where they may be combined to form a ring), C = O, O, S, SO, SO ₂ , or NR ⁹⁷ (where R ⁹⁷ is a hydrogen atom or Represents an alkyl group that may have a branched structure having 1 to 10 carbon atoms).
X ¹ and X ² are independent of each other and may have a single bond, a branched structure having 1 to 10 carbon atoms, or an alkylene group of the formula (14).

(In the formula, R ^{98 to} R ¹⁰¹ are independent of each other and may have a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, a branched structure having 1 to 10 carbon atoms, or an alkyl group having 1 carbon atom. Represents an alkoxy group which may have a branched structure of 10 to 10.
Y ¹ and Y ² represent an alkylene group which may have a single bond or a branched structure having 1 to 10 carbon atoms independently of each other. ) Represents a group. ]
2. 2. A triazine ring-containing polymer in which ^{1 to} R ⁹² and R ^{98 to} R ¹⁰¹ are hydrogen atoms,
3. 3. The triazine ring-containing polymer of 1 or 2 represented by the formula (15), wherein the fluorine atom-containing arylamino group is used.

(In the formula, R ¹⁰² represents a fluorine atom or a fluoroalkyl group having 1 to 10 carbon atoms.)
4. The triazine ring-containing polymer of formula (16), wherein the fluorine atom-containing arylamino group is represented by the formula (16).

(In the formula, R ¹⁰² has the same meaning as described above.)
5. A triazine ring-containing polymer having 3 or 4 carbon atoms in which R ¹⁰² is a perfluoroalkyl group having 1 to 10 carbon atoms.
6. The triazine ring-containing polymer according to any one of 1 to 5 represented by the formula (17), wherein Ar is

7. A film-forming composition containing any of the triazine ring-containing polymers 1 to 6 and an organic solvent.
8. 7. The film-forming composition of 7, wherein the organic solvent is at least one selected from a glycol ester solvent, a ketone solvent, and an ester solvent.
9. 7 or 8 film-forming compositions further comprising a cross-linking agent,
10. The film-forming composition of 9, wherein the cross-linking agent is a polyfunctional (meth) acrylic compound.
11. A thin film obtained from any of the film-forming compositions of 7 to 10.
12. An electronic device comprising a substrate and 11 thin films formed on the substrate,
13. Provided is an optical member including a base material and 11 thin films formed on the base material.

According to the present invention, a triazine ring-containing polymer capable of forming a thin film having a high refractive index and excellent transparency and having excellent solubility in various organic solvents such as a low polar solvent, a hydrophobic solvent, and a low boiling point solvent. Can be provided.
In general, it is known that the refractive index tends to decrease by introducing a fluorine atom into a compound, but the triazine ring-containing polymer of the present invention also has a fluorine atom introduced. Nevertheless, it maintains a refractive index of over 1.7.
By using such a triazine ring-containing polymer of the present invention, a composition can be prepared using an organic solvent having a low dissolving power such as a low polar solvent and a hydrophobic solvent, so that the group is easily eroded by a high polar solvent. A thin film can be formed on the material without any problem.
Since the thin film transistor produced from the film-forming composition of the present invention can exhibit the characteristics of high heat resistance, high refractive index, and low volume shrinkage, a liquid crystal display, an organic electroluminescence (EL) display, a touch panel, and an optical semiconductor ( Electronic devices such as LED) elements, solid-state imaging elements, organic thin-film solar cells, dye-sensitized solar cells, organic thin-film transistors (TFTs), lenses, prisms, cameras, binoculars, microscopes, semiconductor exposure equipment, etc. And can be suitably used in the field of optical materials.
In particular, since the thin film produced from the film-forming composition of the present invention has high transparency and high refractive index, its visibility is improved by using it as a protective film for a transparent conductive film such as ITO or silver nanowires. At the same time, the deterioration can be suppressed.

It is ¹ H-NMR spectrum figure of the polymer compound [4] obtained in Example 1-1.

Hereinafter, the present invention will be described in more detail.
The triazine ring-containing polymer according to the present invention contains a repeating unit structure represented by the following formula (1).

In the above formula, R and R'represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group independently of each other, but both may be hydrogen atoms from the viewpoint of further increasing the refractive index. preferable.
In the present invention, the number of carbon atoms of the alkyl group is not particularly limited, but 1 to 20 is preferable, and 1 to 10 carbon atoms are more preferable in consideration of further enhancing the heat resistance of the polymer. Is even more preferable. Further, the structure may be chain-shaped, branched or annular.

Specific examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, s-butyl, t-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl. , N-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2 , 2-Dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3- Dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl -N-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl -N-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl -N-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1 -Ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2 , 4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2 , 2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclo Examples thereof include propyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl group and the like.

The carbon number of the alkoxy group is not particularly limited, but 1 to 20 is preferable, and considering that the heat resistance of the polymer is further enhanced, the carbon number of 1 to 10 is more preferable, and 1 to 3 is further more preferable. preferable. Further, the structure of the alkyl portion may be chain-like, branched or cyclic.

Specific examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n. -Butoxy, 3-Methyl-n-Butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n -Hexyloxy, 1-methyl-n-pentyloxy, 2-methyl-n-pentyloxy, 3-methyl-n-pentyloxy, 4-methyl-n-pentyloxy, 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-Ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2-trimethyl-n-propoxy, 1-ethyl-1-methyl-n- Examples thereof include propoxy and 1-ethyl-2-methyl-n-propoxy groups.

The number of carbon atoms of the aryl group is not particularly limited, but 6 to 40 is preferable, and 6 to 16 carbon atoms are more preferable and 6 to 13 carbon atoms are further more preferable in consideration of further enhancing the heat resistance of the polymer. preferable.
Specific examples of the aryl group include phenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-fluorophenyl, o-methoxyphenyl, p-methoxyphenyl, p-nitrophenyl, and the like. p-Cyanophenyl, α-naphthyl, β-naphthyl, o-biphenylyl, m-biphenylyl, p-biphenylyl, 1-anthryl, 2-anthryl, 9-anthril, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4 -Phenyl trill, 9-phenyl group and the like can be mentioned.

The carbon number of the aralkyl group is not particularly limited, but it is preferably 7 to 20 carbon atoms, and the alkyl moiety thereof may be linear, branched, or cyclic.
Specific examples thereof include benzyl, p-methylphenylmethyl, m-methylphenylmethyl, o-ethylphenylmethyl, m-ethylphenylmethyl, p-ethylphenylmethyl, 2-propylphenylmethyl, 4-isopropylphenylmethyl, Examples thereof include 4-isobutylphenylmethyl and α-naphthylmethyl groups.

The Ar represents at least one selected from the group represented by the formulas (2) to (13).

The R ^{1 to} R ⁹² are independent of each other and have a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. Representing an alkoxy group which may have a branched structure, R ⁹³ and R ⁹⁴ represent a hydrogen atom or an alkyl group which may have a branched structure having 1 to 10 carbon atoms, and W ¹ and W ² represent a branched structure. , Independent of each other, single bond, CR ⁹⁵ R ⁹⁶ (R ⁹⁵ and R ⁹⁶ may have a branched structure of hydrogen atoms or 1 to 10 carbon atoms independently of each other (provided that they have a branched structure). Represents (which may form a ring together)), C = O, O, S, SO, SO ₂ , or NR ⁹⁷ (R ⁹⁷ is a hydrogen atom or 1 to 10 carbon atoms. Represents an alkyl group that may have a branched structure).
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the alkyl group and the alkoxy group include the same as above.
Further, X ¹ and X ² represent an alkylene group which may have a single bond, a branched structure having 1 to 10 carbon atoms, or a group represented by the formula (14) independently of each other.

The R ^{98 to} R ¹⁰¹ are independent of each other and have a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. Representing an alkoxy group which may have a branched structure, Y ¹ and Y ² represent an alkylene group which may have a single bond or a branched structure having 1 to 10 carbon atoms independently of each other. Examples of these halogen atoms, alkyl groups, and alkoxy groups include the same as above.
Examples of the alkylene group which may have a branched structure having 1 to 10 carbon atoms include methylene, ethylene, propylene, trimethylene, tetramethylene, and pentamethylene group.

Among these, R ^{1 to} R ⁹² and R ^{98 to} R ¹⁰¹ include a hydrogen atom, a halogen atom, a sulfo group, an alkyl group which may have a branched structure having 1 to 5 carbon atoms, or 1 to 1 carbon atoms. An alkoxy group which may have a branched structure of 5 is preferable, and a hydrogen atom is more preferable.

In particular, as Ar, at least one type represented by the formulas (2), (5) to (13) is preferable, and the formulas (2), (5), (7), (8), (11) to (13). ) Is more preferable. Specific examples of the aryl group represented by the above formulas (2) to (13) include, but are not limited to, those represented by the following formulas.

Among these, the aryl group represented by the following formula is more preferable because a polymer having a higher refractive index can be obtained.

In particular, in consideration of further enhancing the solubility of the triazine ring-containing polymer in an organic solvent such as a low-polarity solvent, the m-phenylene group represented by the formula (17) is preferable as Ar.

Further, the triazine ring-containing polymer of the present invention has at least one triazine ring terminal, and at least a part of the triazine ring terminal is sealed with a fluorine atom-containing arylamino group.
Examples of the aryl group include the same as above, but a phenyl group is particularly preferable.
Examples of the fluorine atom-containing group include a fluorine atom-containing hydrocarbon group such as a fluorine atom and a fluoroalkyl group, and a fluorine atom and a fluoroalkyl group having 1 to 10 carbon atoms are preferable.
The fluoroalkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic, and may be, for example, a trifluoromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group or a heptafluoropropyl group. , 2,2,3,3,3-pentafluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,2-trifluoro-1- (trifluoromethyl) ethyl group, nonafluoro Butyl group, 4,4,4-trifluorobutyl group, undecafluoropentyl group, 2,2,3,3,4,5,5,5-nonafluoropentyl group, 2,2,3,3 , 4,4,5,5-octafluoropentyl group, tridecafluorohexyl group, 2,2,3,3,4,5,5,6,6-6-undecafluorohexyl group, 2, Examples thereof include 2,3,3,4,4,5,5,6-decafluorohexyl group, 3,3,4,4,5,5,6,6,6-nonafluorohexyl group.

In particular, in consideration of increasing the solubility of the triazine ring-containing polymer in a low polar solvent or the like while maintaining the refractive index, a perfluoroalkyl group having 1 to 10 carbon atoms is preferable, and a perfluoroalkyl group having 1 to 5 carbon atoms is particularly preferable. Fluoroalkyl groups are more preferred, and trifluoromethyl groups are optimal.

The number of fluorine atom-containing groups is not particularly limited and may be any number that can be substituted on the aryl group, but considering the balance between the maintenance of the refractive index and the solubility in the solvent, 1 to 4 The number is preferable, one or two is more preferable, and one is even more preferable.

Examples of suitable fluorine atom-containing arylamino groups include those represented by the formula (15), and in particular, those represented by the formula (16) having a fluorine atom-containing group at the para position with respect to the amino group are preferable.

（式中、Ｒ¹⁰²は、フッ素原子または炭素数１〜１０のフルオロアルキル基を表す。）

(In the formula, R ¹⁰² represents a fluorine atom or a fluoroalkyl group having 1 to 10 carbon atoms.)

（式中、Ｒ¹⁰²は、上記と同じ意味を表す。）

(In the formula, R ¹⁰² has the same meaning as above.)

Specific examples of the fluorine atom-containing arylamino group include those represented by the following formulas, but are not limited thereto.

The fluorine atom-containing arylamino group can be introduced by using the corresponding fluorine atom-containing arylamino compound in the production method described later.
Specific examples of the fluorine atom-containing arylamino compound include 4-fluoroaniline, 4-trifluoromethylaniline, 4-pentafluoroethylaniline and the like.

In the present invention, particularly suitable triazine ring-containing polymers include those represented by the formulas (18) to (21).

（式中、Ｒ，Ｒ′、Ｒ^１〜Ｒ^４、およびＲ¹⁰²は、上記と同じ意味を表す。）

(In the equation, R, R', R ^{1 to} R ⁴ , and R ¹⁰² have the same meanings as above.)

（式中、Ｒ^１〜Ｒ^４およびＲ¹⁰²は、上記と同じ意味を表す。）

^(Wherein, R 1 to R ⁴ and R ¹⁰² represent the same meaning as above.)

（式中、Ｒ¹⁰²は、上記と同じ意味を表す。）

(In the formula, R ¹⁰² has the same meaning as above.)

（式中、Ｒ¹⁰²は、上記と同じ意味を表す。）

(In the formula, R ¹⁰² has the same meaning as above.)

The weight average molecular weight of the polymer in the present invention is not particularly limited, but is preferably 500 to 500,000, more preferably 500 to 100,000, further improving heat resistance and lowering the shrinkage rate. From this point of view, 2,000 or more is preferable, 50,000 or less is preferable, and 30,000 or less is more preferable, and 10,000 or less is preferable from the viewpoint of further increasing the solubility and lowering the viscosity of the obtained solution. Even more preferable.
The weight average molecular weight in the present invention is the average molecular weight obtained in terms of standard polystyrene by gel permeation chromatography (hereinafter referred to as GPC) analysis.

The triazine ring-containing polymer (hyperbranched polymer) of the present invention can be produced according to the method disclosed in Patent Document 1 described above.
For example, as shown in Scheme 1 below, the triazine ring-containing polymer (20) is prepared by reacting the triazine compound (22) and the aryldiamino compound (23) in a suitable organic solvent and then using an end-capping agent. It can be obtained by reacting with a certain fluorine atom-containing aniline compound (24).

（式中、Ｘは、互いに独立してハロゲン原子を表し、Ｒ¹⁰²は、上記と同じ意味を表す。）

(In the equation, X represents a halogen atom independently of each other, and R ¹⁰² has the same meaning as above.)

In the above reaction, the charging ratio of the aryldiamino compound (23) is arbitrary as long as the desired polymer can be obtained, but the aryldiamino compound (23) 0.01 to 10 per 1 equivalent of the triazine compound (22). Equivalents are preferred, more preferably 1-5 equivalents.
The aryldiamino compound (23) may be added neatly or in a solution dissolved in an organic solvent, but the latter method is preferable in consideration of ease of operation and controllability of the reaction. ..
The reaction temperature may be appropriately set in the range from the melting point of the solvent to be used to the boiling point of the solvent, and is particularly preferably about -30 to 150 ° C, more preferably -10 to 100 ° C.

As the organic solvent, various solvents usually used in this kind of reaction can be used, for example, tetrahydrofuran, dioxane, dimethylsulfoxide; N, N-dimethylformamide, N-methyl-2-pyrrolidone, tetramethylurea, etc. Hexamethylphosphoramide, N, N-dimethylacetamide, N-methyl-2-piperidone, N, N-dimethylethyleneurea, N, N, N', N'-tetramethylmalonic acid amide, N-methylcaprolactam, N-Acetylpyrrolidin, N, N-diethylacetamide, N-ethyl-2-pyrrolidone, N, N-dimethylpropionic acid amide, N, N-dimethylisobutylamide, N-methylformamide, N, N'-dimethylpropylene urea And other amide-based solvents, and mixed solvents thereof.
Of these, N, N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, and a mixture thereof are preferable, and N, N-dimethylacetamide and N-methyl-2-pyrrolidone are particularly preferable. Is preferable.

Further, in the first step reaction of the above scheme 1, various bases usually used at the time of polymerization or after polymerization may be added.
Specific examples of this base include potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, sodium ethoxydo, sodium acetate, lithium carbonate, lithium hydroxide, lithium oxide, potassium acetate, magnesium oxide, and oxidation. Calcium, barium hydroxide, trilithium phosphate, trisodium phosphate, tripotassium phosphate, cesium fluoride, aluminum oxide, ammonia, n-propylamine, trimethylamine, triethylamine, diisopropylamine, diisopropylethylamine, N-methylpiperidine, Examples thereof include 2,2,6,6-tetramethyl-N-methylpiperidin, pyridine, 4-dimethylaminopyridine, N-methylmorpholin and the like.
The amount of the base added is preferably 1 to 100 equivalents, more preferably 1 to 10 equivalents, relative to 1 equivalent of the triazine compound (22). In addition, these bases may be used as an aqueous solution.
It is preferable that no raw material component remains in the obtained polymer, but some raw materials may remain as long as the effects of the present invention are not impaired.
After completion of the reaction, the product can be easily purified by a reprecipitation method or the like.

As a terminal sealing method using the fluorine atom-containing aniline compound (24), a known method may be adopted.
In this case, the amount of the end-capping agent used is preferably about 0.05 to 10 equivalents, more preferably 0.1 to 5 equivalents, relative to 1 equivalent of a halogen atom derived from a surplus triazine compound that was not used in the polymerization reaction. Preferably, 0.5 to 2 equivalents are even more preferred.
The reaction solvent and the reaction temperature include the same conditions as described in the first step reaction of the above scheme 1, and the terminal encapsulant may be charged at the same time as the aryldiamino compound (23).
In addition, you may use an arylamino compound having no fluorine atom and end-seal with two or more kinds of groups. Examples of the aryl group of the arylamino compound having no substituent include the same as above.

The above-mentioned triazine ring-containing polymer of the present invention can be suitably used as a film-forming composition, and in this case, a cross-linking agent may be added.
The cross-linking agent is not particularly limited as long as it is a compound having a substituent capable of reacting with the above-mentioned triazine ring-containing polymer.
Such compounds include melamine compounds having a cross-linking substituent such as a methylol group and a methoxymethyl group, substituted urea compounds, compounds containing a cross-linking substituent such as an epoxy group or an oxetane group, and blocked isocyanates. Examples thereof include compounds containing, compounds having an acid anhydride, compounds having a (meth) acrylic group, phenoplast compounds, etc., but from the viewpoint of heat resistance and storage stability, epoxy groups, blocked isocyanate groups, (meth) acrylics, etc. Group-containing compounds are preferred, and in particular, compounds having a blocked isocyanate group, polyfunctional epoxy compounds and / or polyfunctional (meth) acrylic compounds that provide a photocurable composition without the use of initiators are preferred.
It should be noted that these compounds need only have at least one cross-linking substituent when used for the terminal treatment of the polymer, and at least two cross-linking substituents when used for the cross-linking treatment between the polymers. Must have.

The polyfunctional epoxy compound is not particularly limited as long as it has two or more epoxy groups in one molecule.
Specific examples thereof include tris (2,3-epoxypropyl) isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4- (epoxyethyl) cyclohexane, glycerol triglycidyl ether, and diethylene glycol diglycidyl. Ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris [p- (2,3-epoxypropoxy) phenyl] propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'- Methylenebis (N, N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylol ethanetriglycidyl ether, bisphenol-A-diglycidyl ether, pentaerythritol polyglycidyl ether, etc. Can be mentioned.

In addition, as commercially available products, YH-434 and YH434L (manufactured by Toto Kasei Co., Ltd.), which are epoxy resins having at least two epoxy groups, and Epolide GT-401 and GT, which are epoxy resins having a cyclohexene oxide structure, are available. -403, GT-301, GT-302, Celoxide 2021, 3000 (manufactured by Daicel Chemical Industry Co., Ltd.), Epicoat (currently jER) 1001, 1002, 1003, which is a bisphenol A type epoxy resin. 1004, 1007, 1009, 1010, 828 (all manufactured by Japan Epoxy Resin Co., Ltd.), Epicoat (currently jER) 807 (currently manufactured by Japan Epoxy Resin Co., Ltd.), which is a bisphenol F type epoxy resin. , Phenol novolac type epoxy resin, Epicoat (currently jER) 152, 154 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPPN201, 202 (above, manufactured by Nippon Kayaku Co., Ltd.), Cresol novolac type Epoxy resins, EOCN-102, 103S, 104S, 1020, 1025, 1027 (all manufactured by Nippon Kayaku Co., Ltd.), Epicoat (currently jER) 180S75 (manufactured by Japan Epoxy Resin Co., Ltd.) ), Denacol EX-252 (manufactured by Nagase ChemteX Corporation), CY175, CY177, CY179 (all manufactured by CIBA-GEIGY AG), Araldite CY-182, CY-192, which are alicyclic epoxy resins. , CY-184 (above, CIBA-GEIGY AG), Epicron 200, 400 (above, DIC Co., Ltd.), Epicoat (currently jER) 871, 872 (above, Japan Epoxy Resin Co., Ltd.) ), ED-5661, ED-5662 (all manufactured by Ceranies Coating Co., Ltd.), Denacol EX-611, EX-612, EX-614, EX-622, which are aliphatic polyglycidyl ethers. , EX-411, EX-512, EX-522, EX-421, EX-313, EX-314, EX-321 (manufactured by Nagase ChemteX Corporation) and the like can also be used. ..

The polyfunctional (meth) acrylic compound is not particularly limited as long as it has two or more (meth) acrylic groups in one molecule.
Specific examples thereof include ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, ethoxylated trimethyl propantriacrylate, and ethoxylated. Trimethylol propantrimethacrylate, glycerin triacrylate ethoxylated, glycerin trimethacrylate ethoxylated, pentaerythritol tetraacrylate ethoxylated, pentaerythritol tetramethacrylate ethoxylated, dipentaerythritol hexaacrylate ethoxylated, polyglycerin monoethylene oxide polyacrylate, polyglycerin Polyethylene glycol polyacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylol propanetriacrylate, trimethylolpropane trimethacrylate , Tricyclodecanedimethanol diacrylate, tricyclodecanedimethanol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, polybasic acid-modified acrylic oligomer and the like.

Further, the polyfunctional (meth) acrylic compound is available as a commercially available product, and specific examples thereof include NK ester A-200, A-400, A-600, A-1000, and A-. 9300 (Tris isocyanurate (2-acryloyloxyethyl)), A-9300-1CL, A-TMPT, UA-53H, 1G, 2G, 3G, 4G, 9G, 14G, 14G 23G, ABE-300, A-BPE-4, A-BPE-6, A-BPE-10, A-BPE-20, A-BPE-30, BPE-80N, BPE- 100N, BPE-200, BPE-500, BPE-900, BPE-1300N, A-GLY-3E, A-GLY-9E, A-GLY-20E, A-TMPT-3EO, A-TMPT-9EO, AT-20E, ATM-4E, ATM-35E (all manufactured by Shin Nakamura Chemical Industry Co., Ltd.), KAYARAD (registered trademark) DPEA-12, PEG400DA, THE-330 , RP-1040 (above, manufactured by Nippon Kayaku Co., Ltd.), Aronix M-210, M-350 (above, manufactured by Toa Synthetic Co., Ltd.), KAYARAD (registered trademark) DPHA, NPGDA, PET30 (above) , Nippon Kayaku Co., Ltd., NK ester A-DPH, A-TMPT, A-DCP, A-HD-N, TMPT, DCP, NPG, HD-N (above, new) Nakamura Chemical Industry Co., Ltd., NK Oligo U-15HA (Shin Nakamura Chemical Industry Co., Ltd.), NK Polymer Vanarezin GH-1203 (Shin Nakamura Chemical Industry Co., Ltd.), DN-0075 (Nippon Kayaku (Nippon Kayaku) Co., Ltd.) and the like.
The above-mentioned polybasic acid-modified acrylic oligomer is also available as a commercially available product, and specific examples thereof include Aronix M-510, 520 (all manufactured by Toagosei Co., Ltd.) and the like.

The acid anhydride compound is not particularly limited as long as it is a carboxylic acid anhydride obtained by dehydrating and condensing two molecules of carboxylic acid, and specific examples thereof include phthalic anhydride, tetrahydrophthalic anhydride, and hexahydroanhydride. One in the molecule such as phthalic acid, methyltetrahydro phthalic anhydride, methylhexahydrophthalic anhydride, nadicic anhydride, methylnadic anhydride, maleic anhydride, succinic anhydride, octyl anhydride, succinic anhydride, dodecenyl succinic anhydride, etc. Those having an acid anhydride group; 1,2,3,4-cyclobutanetetracarboxylic dianhydride, pyromellitic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene Succinic hydride, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic hydride, 5- (2,5-dioxotetrahydro-3-franyl) -3-methyl -3-Cyclohexene-1,2-dicarboxylic acid anhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, 3, 3', 4,4'-biphenyltetracarboxylic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-dimethyl-1,2,3,4 -Cyclobutanetetracarboxylic acid dianhydride and the like having two acid anhydride groups in the molecule and the like can be mentioned.

As a compound containing blocked isocyanate, if an isocyanate group (-NCO) has two or more blocked isocyanate groups in one molecule blocked by an appropriate protective group and is exposed to a high temperature during thermal curing. , The group is not particularly limited as long as the protective group (block portion) is thermally dissociated and detached, and the generated isocyanate group causes a cross-linking reaction with the resin. For example, one group represented by the following formula is used. Examples thereof include compounds having two or more (note that these groups may be the same or different from each other) in the molecule.

（式中、Ｒ_bはブロック部の有機基を表す。）

(In the formula, R _b represents the organic group in the block portion.)

Such a compound can be obtained, for example, by reacting a compound having two or more isocyanate groups in one molecule with an appropriate blocking agent.
Examples of the compound having two or more isocyanate groups in one molecule include isophorone diisocyanate, 1,6-hexamethylene diisocyanate, methylenebis (4-cyclohexamethylene diisocyanate), polyisocyanate of trimethylhexamethylene diisocyanate, and dimer thereof. , Trimers, and reactants of these with diols, triols, diamines, or triamines.
Examples of the blocking agent include alcohols such as methanol, ethanol, isopropanol, n-butanol, 2-ethoxyhexanol, 2-N, N-dimethylaminoethanol, 2-ethoxyethanol, cyclohexanol; phenol, o-nitrophenol. , P-Chlorophenol, o-, m- or p-cresol and other phenols; ε-caprolactam and other lactams, acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanol oxime, acetophenone oxime, benzophenone oxime and other oximes. Classes; pyrazoles such as pyrazole, 3,5-dimethylpyrazole and 3-methylpyrazole; thiols such as dodecanethiol and benzenethiol.

Compounds containing blocked isocyanate are also available as commercial products, and specific examples thereof include B-830, B-815N, B-842N, B-870N, B-874N, B-882N, and B. -7005, B-7030, B-7075, B-5010 (all manufactured by Mitsui Chemicals Polyurethane Co., Ltd.), Duranate (registered trademark) 17B-60PX, TPA-B80E, MF-B60X, MF-K60X, E402-B80T (above, manufactured by Asahi Kasei Chemicals Co., Ltd.), Karenz MOI-BM (registered trademark) (above, manufactured by Showa Denko KK), BI-7950, BI-7951, BI-7960, BI-7961, Examples thereof include BI-7963, BI-7982, BI-7991, BI-7992 (manufactured by Baxenden chemicals LTD) and the like.

The aminoplast compound is not particularly limited as long as it has two or more methoxymethylene groups in one molecule. For example, hexamethoxymethylmelamine CYMEL (registered trademark) 303 and tetrabutoxymethylglycolyl uryl 1170. , Tetramethoxymethylbenzoguanamine 1123 (all manufactured by Nippon Cytec Industries Co., Ltd.), etc., Nikalac (registered trademark) MW-30HM, MW-390, MW-100LM, which is a methylated melamine resin. Examples thereof include melamine compounds such as MX-750LM, MX-270 which is a methylated urea resin, MX-280 and MX-290 (all manufactured by Sanwa Chemical Co., Ltd.) and the like.
The oxetane compound is not particularly limited as long as it has two or more oxetanyl groups in one molecule, and is, for example, OXT-221, OX-SQ-H, OX-SC (or more) containing an oxetane group. , Toagosei Co., Ltd.) and the like.

A phenoplast compound has two or more hydroxymethylene groups in one molecule, and when exposed to a high temperature during thermosetting, a cross-linking reaction proceeds by a dehydration condensation reaction with the polymer of the present invention. Is.
Examples of the phenoplast compound include 2,6-dihydroxymethyl-4-methylphenol, 2,4-dihydroxymethyl-6-methylphenol, bis (2-hydroxy-3-hydroxymethyl-5-methylphenyl) methane, and the like. Bis (4-hydroxy-3-hydroxymethyl-5-methylphenyl) methane, 2,2-bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane, bis (3-formyl-4-hydroxyphenyl) methane , Bis (4-hydroxy-2,5-dimethylphenyl) formylmethane, α, α-bis (4-hydroxy-2,5-dimethylphenyl) -4-formyltoluene and the like.
The phenoplast compound is also available as a commercial product, and specific examples thereof include 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, and BI25X-DF. , BI25X-TPA (all manufactured by Asahi Organic Materials Industry Co., Ltd.) and the like.

Among these, a polyfunctional (meth) acrylic compound is preferable because it can suppress a decrease in the refractive index due to the addition of a cross-linking agent and the curing reaction proceeds rapidly. Among these, a triazine ring-containing polymer is suitable. A polyfunctional (meth) acrylic compound having the following isocyanuric acid skeleton is more preferable because of its excellent compatibility.
Examples of the polyfunctional (meth) acrylic compound having such a skeleton include NK ester A-9300 and A-9300-1CL (both manufactured by Shin Nakamura Chemical Industry Co., Ltd.).

（式中、Ｒ¹¹¹〜Ｒ¹¹³は、互いに独立して、末端に少なくとも１つの（メタ）アクリル基を有する一価の有機基である。）

(In the formula, R ^{111 to} R ¹¹³ are monovalent organic groups having at least one (meth) acrylic group at the end, independent of each other.)

Further, from the viewpoint of further improving the curing rate and enhancing the solvent resistance, acid resistance, and alkali resistance of the obtained cured film, it is liquid at 25 ° C. and its viscosity is 5000 mPa · s or less, preferably 1. A polyfunctional (meth) acrylic compound of ~ 3000 mPa · s, more preferably 1 to 1000 mPa · s, even more preferably 1 to 500 mPa · s (hereinafter referred to as a low-viscosity cross-linking agent) is used alone or in combination of two or more. Alternatively, it is preferably used in combination with the above-mentioned polyfunctional (meth) acrylic compound having an isocyanuric acid skeleton.
Such low-viscosity cross-linking agents are also available as commercial products. For example, among the above-mentioned polyfunctional (meth) acrylic compounds, NK ester A-GLY-3E (85 mPa · s, 25 ° C.), A-GLY. -9E (95 mPa · s, 25 ° C), A-GLY-20E (200 mPa · s, 25 ° C), A-TMPT-3EO (60 mPa · s, 25 ° C), A-TMPT-9EO, ATM The chain length between (meth) acrylic groups of -4E (150 mPa · s, 25 ° C), ATM-35E (350 mPa · s, 25 ° C) (above, manufactured by Shin Nakamura Chemical Industry Co., Ltd.) is relatively long. Long cross-linking agents can be mentioned.

Further, considering that the alkali resistance of the obtained cured film is also improved, NK ester A-GLY-20E (manufactured by Shin Nakamura Chemical Industry Co., Ltd.) and ATM-35E (manufactured by Shin Nakamura Chemical Industry Co., Ltd.) ), And the above-mentioned polyfunctional (meth) acrylic compound having an isocyanuric acid skeleton are preferably used in combination.

Further, when a thin film made of the triazine ring-containing polymer of the present invention is laminated on a protective film such as PET or a polyolefin film and light is irradiated through the protective film, the thin film laminated film also cures well without being affected by oxygen. You can get sex. In this case, since the protective film needs to be peeled off after curing, it is preferable to use a polybasic acid-modified acrylic oligomer that gives a thin film having good peelability.

The above-mentioned cross-linking agent may be used alone or in combination of two or more. The amount of the cross-linking agent used is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the triazine ring-containing polymer, but the lower limit thereof is preferably 2 parts by mass, more preferably 5 parts by mass in consideration of solvent resistance. Further, in consideration of controlling the refractive index, the upper limit thereof is preferably 20 parts by mass, more preferably 15 parts by mass.

Initiators corresponding to the respective cross-linking agents can also be blended in the composition of the present invention. As described above, when a polyfunctional epoxy compound and / or a polyfunctional (meth) acrylic compound is used as the cross-linking agent, photocuring proceeds to give a cured film without using an initiator. Initiators may be used in some cases.

When a polyfunctional epoxy compound is used as a cross-linking agent, a photoacid generator or a photobase generator can be used.
As the photoacid generator, a known one may be appropriately selected and used, and for example, an onium salt derivative such as a diazonium salt, a sulfonium salt or an iodonium salt can be used.
Specific examples thereof include aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate and 4-methylphenyldiazonium hexafluorophosphate; diphenyliodonium hexafluoroantimonate and di (4-methylphenyl). Diaryliodonium salts such as iodonium hexafluorophosphate, di (4-tert-butylphenyl) iodonium hexafluorophosphate; triphenylsulfonium hexafluoroantimonate, tris (4-methoxyphenyl) sulfonium hexafluorophosphate, diphenyl-4-thiophenoxy Phenylsulfonium hexafluoroantimonate, diphenyl-4-thiophenoxyphenylsulfonium hexafluorophosphate, 4,4'-bis (diphenylsulfonio) phenylsulfide-bishexafluoroantimonate, 4,4'-bis (diphenylsulfoni) E) Phenylsulfide-bishexafluorophosphate, 4,4'-bis [di (β-hydroxyethoxy) phenylsulfonio] phenylsulfide-bishexafluoroantimonate, 4,4'-bis [di (β-hydroxyethoxy) di (β-hydroxyethoxy) ) Phenylsulfonio] Phenylsulfide-bis-hexafluorophosphate, 4- [4'-(benzoyl) phenylthio] phenyl-di (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- [4'-(benzoyl) phenylthio ] Examples thereof include triarylsulfonium salts such as phenyl-di (4-fluorophenyl) sulfonium hexafluorophosphate.

Commercially available products may be used as these onium salts, and specific examples thereof include Sun Aid SI-60, SI-80, SI-100, SI-60L, SI-80L, SI-100L, SI-L145, SI-. L150, SI-L160, SI-L110, SI-L147 (above, manufactured by Sanshin Chemical Industry Co., Ltd.), UVI-6950, UVI-6970, UVI-6974, UVI-6990, UVI-6992 (above, Union Carbide) CPI-100P, CPI-100A, CPI-200K, CPI-200S (manufactured by Sun Appro Co., Ltd.), Adecocaopter SP-150, SP-151, SP-170, SP-171 (manufactured by Sun Appro Co., Ltd.) Asahi Denka Kogyo Co., Ltd.), Irgacure 261 (BASF), CI-2481, CI-2624, CI-2369, CI-2064 (above, Nippon Soda Co., Ltd.), CD-1010, CD-1011 , CD-1012 (all manufactured by Sartmer), DS-100, DS-101, DAM-101, DAM-102, DAM-105, DAM-201, DSM-301, NAI-100, NAI-101, NAI- 105, NAI-106, SI-100, SI-101, SI-105, SI-106, PI-105, NDI-105, BENZOIN TOSYLATE, MBZ-101, MBZ-301, PYR-100, PYR-200, DNB -101, NB-101, NB-201, BBI-101, BBI-102, BBI-103, BBI-109 (all manufactured by Midori Chemical Co., Ltd.), PCI-061T, PCI-062T, PCI-020T, PCI -022T (all manufactured by Nippon Kayaku Co., Ltd.), IBPF, IBCF (manufactured by Sanwa Chemical Co., Ltd.) and the like can be mentioned.

On the other hand, the photobase generator may be appropriately selected from known ones and used, for example, a Co-amine complex type, an oxime carboxylic acid ester type, a carbamic acid ester type, a quaternary ammonium salt type photobase generator and the like. Can be used.
Specific examples thereof include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, and bis [[(2). -Nitrobenzyl) oxy] carbonyl] hexane 1,6-diamine, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoetan, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, N- (2-Nitrobenzyloxycarbonyl) pyrrolidine, hexaammine cobalt (III) tris (triphenylmethylborate), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2,6-dimethyl- 3,5-Diacetyl-4- (2'-nitrophenyl) -1,4-dihydropyridine, 2,6-dimethyl-3,5-diacetyl-4- (2', 4'-dinitrophenyl) -1,4 − Dihydropyridine and the like.
Further, a commercially available product may be used as the photobase generator, and specific examples thereof include TPS-OH, NBC-101, ANC-101 (all product names, manufactured by Midori Chemical Co., Ltd.) and the like.

When a photoacid or a base generator is used, it is preferably used in the range of 0.1 to 15 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the polyfunctional epoxy compound.
If necessary, the epoxy resin curing agent may be added in an amount of 1 to 100 parts by mass with respect to 100 parts by mass of the polyfunctional epoxy compound.

On the other hand, when a polyfunctional (meth) acrylic compound is used, a photoradical polymerization initiator can be used.
As the photoradical polymerization initiator, it may be appropriately selected from known ones and used, for example, acetophenones, benzophenones, Michler's benzoylbenzoate, amyroxime ester, oxime ester, tetramethylthium monosulfide, thioxanthone and the like. Can be mentioned.
In particular, a photocleavable photoradical polymerization initiator is preferable. The photocleavable photoradical polymerization initiator is described in the latest UV curing technology (page 159, publisher: Kazuhiro Takausu, publisher: Technical Information Association, 1991).
Examples of commercially available photoradical polymerization initiators include BASF's trade names: Irgacure 127, 184, 369, 379, 379EG, 651, 500, 754, 819, 903, 907, 784, 2959, CGI1700, CGI1750, CGI1850. , CG24-61, OXE01, OXE02, DaroCure 1116, 1173, MBF, BASF Product Name: Lucillin TPO, UCB Product Name: Yubekrill P36, Flateturi Lamberti Product Name: EzaCure KIP150, KIP65LT, KIP100F Examples thereof include KT37, KT55, KTO46, and KIP75 / B.
When a photoradical polymerization initiator is used, it is preferably used in the range of 0.1 to 200 parts by mass, preferably in the range of 1 to 150 parts by mass with respect to 100 parts by mass of the polyfunctional (meth) acrylate compound. Is more preferable.

Further, a polyfunctional thiol compound having two or more mercapto groups in the molecule may be added to the composition of the present invention for the purpose of accelerating the reaction between the triazine ring-containing polymer and the cross-linking agent. Good.
Specifically, a polyfunctional thiol compound represented by the following formula is preferable.

The above L represents a 2-4 valent organic group, preferably an aliphatic group having 2 to 4 valences of 2 to 12 carbon atoms or a heterocyclic group containing 2 to 4 valences, and 2 to 4 valent carbon atoms. More preferably, an aliphatic group of ~ 8 or a trivalent group having an isocyanuric acid skeleton (1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione ring) represented by the following formula is preferable. ..
The above n represents an integer of 2 to 4 corresponding to the valence of L.

（式中、「・」は、酸素原子との結合部を示す。）

(In the formula, "・" indicates the bond with the oxygen atom.)

Specific compounds include 1,4-bis (3-mercaptobutylyloxy) butane and 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4. , 6- (1H, 3H, 5H) -trione, pentaerythritol tetrakis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolethane ethanetris (3-mercaptobutyrate), etc. Be done.
These polyfunctional thiol compounds can also be obtained as commercial products, and examples thereof include Karenz MT-BD1, Karenz MT NR1, Karenz MT PE1, TPMB, and TEMB (all manufactured by Showa Denko KK).
These polyfunctional thiol compounds may be used alone or in combination of two or more.

When a polyfunctional thiol compound is used, the amount added thereof is not particularly limited as long as it does not adversely affect the obtained thin film, but in the present invention, 0.01 to 10% by mass in 100% by mass of solid content. % Is preferable, and 0.03 to 6% by mass is more preferable.

It is preferable to add various solvents to the composition of the present invention to dissolve the triazine ring-containing polymer before use.
Examples of the solvent include water, toluene, p-xylene, o-xylene, m-xylene, ethylbenzene, styrene, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol, propylene glycol monoethyl ether, and ethylene. Glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol methyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl Ether, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol, 1-octanol, ethylene glycol, hexylene glycol, trimethylene glycol, 1-methoxy- 2-butanol, cyclohexanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, propylene glycol, benzyl alcohol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, γ-butyrolactone , Acetone, methyl ethyl ketone, methyl isopropyl ketone, diethyl ketone, methyl isobutyl ketone, methyl normal butyl ketone, cyclopentanone, cyclohexanone, ethyl acetate, isopropyl acetate, normal propyl acetate, isobutyl acetate, normal butyl acetate, ethyl lactate, methanol, ethanol , Isopropanol, tert-butanol, allyl alcohol, normal propanol, 2-methyl-2-butanol, isobutanol, normal butanol, 2-methyl-1-butanol, 1-pentanol, 2-methyl-1-pentanol, 2 -Ethylhexanol, 1-methoxy-2-propanol, tetrahydrofuran, 1,4-dioxane, N, N-dimethylformamide, N, N-dimethylacetamide (DMAc), N-methylpyrrolidone, 1,3-dimethyl-2- Imidazo Examples thereof include lydinone, dimethyl sulfoxide, N-cyclohexyl-2-pyrrolidinone, etc., and these may be used alone or in combination of two or more.

As described above, since the triazine ring-containing polymer of the present invention has excellent solubility in organic solvents, glycols such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate, and diethylene glycol monoethyl ether acetate Ester solvent; Ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, diacetone alcohol; ethyl acetate, methyl acetate, butyl acetate, methoxybutyl acetate, cellosolve acetate, amyl acetate, acetic acid Since it dissolves well in ester solvents such as normal propyl, isopropyl acetate, methyl lactate, ethyl lactate, and butyl lactate, it is particularly suitable for forming a thin film at a site where these solvents are required.

At this time, the solid content concentration in the composition is not particularly limited as long as it does not affect the storage stability, and may be appropriately set according to the thickness of the target film. Specifically, from the viewpoint of solubility and storage stability, the solid content concentration is preferably 0.1 to 50% by mass, more preferably 0.1 to 40% by mass.

The composition of the present invention contains other components other than the triazine ring-containing polymer, the cross-linking agent and the solvent, for example, a leveling agent, a surfactant, a silane coupling agent, and inorganic fine particles, as long as the effects of the present invention are not impaired. Additives such as may be included.
Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octylphenol ether, and polyoxyethylene nonylphenol. Polyoxyethylene alkylallyl ethers such as ether; polyoxyethylene / polyoxypropylene block copolymers; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Such as sorbitan fatty acid esters; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc. Nonionic surfactants such as sorbitan fatty acid esters, trade names Ftop EF301, EF303, EF352 (manufactured by Mitsubishi Materials Denshi Kasei Co., Ltd. (formerly manufactured by Gemco Co., Ltd.)), trade names Megafuck F171, F173, R- 08, R-30, R-40, F-553, F-554, RS-75, RS-72-K (manufactured by DIC Co., Ltd.), Florard FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), trade name Fluorine-based surfactants such as Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), Organosiloxane polymer KP341 (manufactured by Shinetsu Chemical Industry Co., Ltd.), BYK -302, BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-370, BYK-375, BYK-378 (manufactured by BIC Chemie Japan Co., Ltd.) and the like.

These surfactants may be used alone or in combination of two or more. The amount of the surfactant used is preferably 0.0001 to 5 parts by mass, more preferably 0.001 to 1 part by mass, and 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the triazine ring-containing polymer. Even more preferable.

The inorganic fine particles include, for example, a group consisting of Be, Al, Si, Ti, V, Fe, Cu, Zn, Y, Zr, Nb, Mo, In, Sn, Sb, Ta, W, Pb, Bi and Ce. Oxides, sulfides or nitrides of one or more metals of choice may be mentioned, and these metal oxides are particularly preferred. The inorganic fine particles may be used alone or in combination of two or more.
Specific examples of the metal oxide include Al ₂ O ₃ , ZnO, TiO ₂ , ZrO ₂ , Fe ₂ O ₃ , Sb ₂ O ₅ , BeO, ZnO, SnO ₂ , CeO ₂ , SiO ₂ , and WO _3. Be done.
It is also effective to use a plurality of metal oxides as the composite oxide. The composite oxide is a mixture of two or more kinds of inorganic oxides at the stage of producing fine particles. For example, TiO ₂ and ZrO ₂ , TiO ₂ and ZrO ₂ and SnO ₂ , and a composite oxide of ZrO ₂ and SnO ₂ can be mentioned.
Further, it may be a compound of the above metal. For example, like _{ZnSb 2 O 6, BaTiO 3,} SrTiO 3, SrSnO 3. These compounds can be used alone or in admixture of two or more, and may be further mixed with the above oxides.
The above other components can be added in any step when preparing the composition of the present invention.

The film-forming composition of the present invention can be applied to a substrate, and then heated to evaporate the solvent, if necessary, and then heated or irradiated with light to obtain a desired cured film.
The coating method of the composition is arbitrary, for example, spin coating method, dip method, flow coating method, inkjet method, jet dispenser method, spray method, bar coating method, gravure coating method, slit coating method, roll coating method, transfer. A printing method, a brush coating method, a blade coating method, an air knife coating method, or the like can be adopted.

Further, as the base material, silicon, glass on which indium tin oxide (ITO) is formed, glass on which indium zinc oxide (IZO) is formed, metal nanowires, polyethylene terephthalate (PET), plastic, glass, etc. Examples thereof include a base material made of quartz, ceramics, etc., and a flexible base material having flexibility can also be used.
The firing temperature is not particularly limited for the purpose of evaporating the solvent, and can be performed at, for example, 110 to 400 ° C.
The firing method is not particularly limited, and for example, it may be evaporated in the atmosphere, an inert gas such as nitrogen, or in an appropriate atmosphere such as in a vacuum using a hot plate or an oven.
For the firing temperature and firing time, conditions suitable for the process process of the target electronic device may be selected, and firing conditions may be selected so that the physical property values of the obtained film match the required characteristics of the electronic device.
The conditions for light irradiation are not particularly limited, and appropriate irradiation energy and time may be adopted depending on the triazine ring-containing polymer and the cross-linking agent used.

Since the thin film transistor and the cured film of the present invention obtained as described above can achieve high heat resistance, high refractive index, and low volume shrinkage, a liquid crystal display, an organic electroluminescence (EL) display, a touch panel, and an optical semiconductor ( Electronic devices such as LED) elements, solid-state imaging elements, organic thin-film solar cells, dye-sensitized solar cells, organic thin-film transistors (TFTs), lenses, prism cameras, binoculars, microscopes, semiconductor exposure equipment, etc. It can be suitably used in the field of optical materials.
In particular, since the thin film or cured film produced from the composition of the present invention has high transparency and high refractive index, its visibility is improved when it is used as a protective film for a transparent conductive film such as ITO or silver nanowires. It can be improved and the deterioration of the transparent conductive film can be suppressed.
As the transparent conductive film, a transparent conductive film having a conductive nanostructure such as an ITO film, an IZO film, metal nanoparticles, metal nanowires, and a metal nanomesh is preferable, and a transparent conductive film having a conductive nanostructure is more preferable. The metal constituting the conductive nanostructure is not particularly limited, and examples thereof include silver, gold, copper, nickel, platinum, cobalt, iron, zinc, ruthenium, rhodium, palladium, cadmium, osmium, iridium, and alloys thereof. That is, a transparent conductive film having silver nanoparticles, silver nanowires, silver nanomesh, gold nanoparticles, gold nanowires, gold nanomesh, copper nanoparticles, copper nanowires, copper nanomesh and the like is preferable, and a transparent conductive film having silver nanowires is particularly preferable. A membrane is preferred.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. The measuring devices used in the examples are as follows.
[ ^{1 1} H-NMR]
Equipment: Varian NMR System 400NB (400MHz)
JEOL-ECA700 (700MHz)
Measuring solvent: DMSO-d6
Reference substance: Tetramethylsilane (TMS) (δ0.0ppm)
[GPC]
Equipment: HLC-8200 GPC manufactured by Tosoh Corporation
Column: Shodex KF-804L + KF-805L
Column temperature: 40 ° C
Solvent: tetrahydrofuran (THF)
Detector: UV (254 nm)
Calibration curve: Standard polystyrene [ellipsometer]
Equipment: Multi-incident angle spectroscopic ellipsometer VASE manufactured by JA Woolam Japan

[1] Synthesis of Triazine Ring-Containing Polymer [Example 1-1] Synthesis of Polymer Compound [4]

After adding m-phenylenediamine [2] (6.00 g, 0.055 mol, manufactured by AminoChem) and 78.88 g of dimethylacetamide (DMAc, manufactured by Junsei Chemical Co., Ltd.) to a 200 mL four-necked flask and replacing with nitrogen. , M-phenylenediamine [2] was dissolved in DMAc. Then, it is cooled to -10 ° C. in an ethanol-dry ice bath, and the bath temperature of 2,4,6-trichloro-1,3,5-triazine [1] (9.22 g, 0.05 mol, manufactured by Eponic Deguza) is adjusted. It was added while confirming that the temperature did not exceed 0 ° C. After stirring for 1 hour, 64.16 g of DMAc was added in advance to the reaction solution, and after nitrogen substitution, the reaction solution was added dropwise to a 500 mL four-necked flask set at 85 ° C. in an oil bath. After stirring for 1 hour, 4-trifluoromethylaniline [3] (23.90 g, 0.15 mol, manufactured by Tianjin Jiahan Chemical Co., Ltd.) was added dropwise, and the mixture was stirred for 3 hours. Then, the temperature was lowered to room temperature, n-propylamine (13.0 g, manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, and the mixture was stirred for 1 hour and then stopped. The reaction solution was added dropwise to ion-exchanged water (910 g) for reprecipitation. The precipitate was filtered and redissolved in THF (73.75 g), the solution being added dropwise to a mixed solution of methanol (300 g) and ion-exchanged water (200 g) and reprecipitated again. The obtained precipitate was filtered and dried in a vacuum drier at 120 ° C. for 6 hours to obtain 16.7 g of the target polymer compound [4] (hereinafter referred to as TDF111). The measurement result of the ¹ H-NMR spectrum of TDF111 is shown in FIG.
The weight average molecular weight Mw measured by GPC of TDF111 in terms of polystyrene was 3,300, and the polydispersity Mw / Mn was 4.4.

When the TDF111 (0.5 g) obtained in Example 1-1 was dissolved in methyl ethyl ketone (4.5 g), methyl isobutyl ketone (4.5 g), and normal propyl acetate (4.5 g), whichever was obtained. It was also dissolved in a solvent to obtain a uniform varnish.

[2] Preparation of film-forming composition and film [Example 2-1]
The TDF111 (4.0 g) obtained in Example 1-1 was dissolved in PGMEA (40.0 g) to prepare a uniform transparent varnish (hereinafter referred to as TDF111V1).
The obtained TDF111V1 was spin-coated on a glass substrate with a spin coater aiming at 500 nm, and fired on a hot plate at 150 ° C. for 2 minutes to obtain a coating film (hereinafter, TDF111F1).
Table 1 shows the refractive index and the film thickness of the TDF111F1 produced in Example 2-1.

As shown in Table 1, it can be seen that the thin film prepared from the polymer compound obtained in Example 1-1 has a refractive index exceeding 1.72.

[3] Preparation of cross-linking agent-added film-forming composition and preparation of cured film [Example 3-1]
TDF111V1 (33.3 g) prepared in Example 2-1 was mixed with ethoxylated glycerin triacrylate (A-GLY-20E, 200 mPa · s, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) in a 1 mass% PGMEA solution as a cross-linking agent. 11.1 g and 1 mass% PGMEA solution ethoxylated pentaerythritol tetraacrylate (ATM-35E, 350 mPa · s, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 3.33 g, 1 mass% PGMEA solution as a photoradical polymerization initiator 8.89 g of Irgacure 184 (manufactured by BASF), 3.33 g of Megafuck R-559 (manufactured by DIC Co., Ltd.) of 1 mass% PGMEA solution as a surfactant, and 60.0 g of PGMEA were added and dissolved visually. After confirmation, a varnish having a solid content of 3% by mass was prepared (referred to as TDF11VF1).
This TDF11VF1 was spin-coated on a non-alkali glass substrate with a spin coater at 200 rpm for 5 seconds and at 1000 rpm for 30 seconds, and fired at 120 ° C. for 3 minutes using an oven. Then, it was cured with a high-pressure mercury lamp at an integrated exposure of 200 mJ / cm ² to prepare a cured film.
When the refractive index of the obtained cured film was measured, the refractive index at 550 nm was 1.730.

[Example 3-2]
TDF111V1 (0.61 g) prepared in Example 2-1 was mixed with ethoxylated glycerin triacrylate (A-GLY-20E, 200 mPa · s, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) in a 1 mass% PGMEA solution as a cross-linking agent. 1.23 g and 1 mass% PGMEA solution ethoxylated pentaerythritol tetraacrylate (ATM-35E, 350 mPa · s, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 0.37 g, 1 mass% PGMEA solution as a photoradical polymerization initiator It was visually dissolved by adding 0.98 g of Irgacure 184 (manufactured by BASF), 0.123 g of Megafuck R-559 (manufactured by DIC Co., Ltd.) of 1 mass% PGMEA solution as a surfactant, and 1.07 g of PGMEA. After confirmation, a varnish having a solid content of 3% by mass was prepared (referred to as TDF11VF2).
A cured film was prepared in the same manner as in Example 3-1 except that this TDF11VF2 was used.
When the refractive index of the obtained cured film was measured, the refractive index at 550 nm was 1.702.

[Example 3-3]
The TDF-111 (20 g) obtained in Example 1-1 was dissolved in 80 g of normal propyl acetate (NPAC) to prepare a 20% by mass solution (hereinafter referred to as TDF-111VP1).
Prepared TDF-111VP1 8.74g, 10% by mass NPAC solution KAYARAD DN-0075 (3000-5000mPa · s, manufactured by Nippon Kayaku Co., Ltd.) 52.41g, 10% by mass NPAC solution ethoxylated pentaerythritol tetraacrylate (ATM-35E, molecular weight 1,892, 350 mPa · s, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 3.49 g, photoradical initiator of 5 mass% propylene glycol monomethyl ether (PGME) solution Irgacure 2959 (manufactured by BASF) 1.40 g, 0.1 mass% NPAC solution Karenz MT NR1 (manufactured by Showa Denko Co., Ltd.) 5.24 g, 1 mass% NPAC solution surfactant Megafuck R-40 (manufactured by DIC Co., Ltd.) 1. 747 g, 35.48 g of NPAC and 41.49 g of PGME were added, and it was confirmed that the solution was visually dissolved to prepare a varnish having a total solid content concentration of 5% by mass (hereinafter referred to as TDF-111VPF1).
This TDF-111VPF1 was spin-coated on a soda lime glass substrate using a spin coater at 200 rpm for 5 seconds and at 1,500 rpm for 30 seconds, and dried at 80 ° C. for 2 minutes using a hot plate. Then, it was cured in the atmosphere with an integrated exposure amount of 600 mJ / cm ² using a high-pressure mercury lamp to obtain a cured film having a film thickness of 250 nm.
When the refractive index of the obtained cured film was measured, the refractive index at 550 nm was 1.558.

In addition, the obtained cured film was subjected to a scratch resistance test using Bencot with a load of 250 g and 10 reciprocations. As a result, it was confirmed by visual inspection and observation with an optical microscope that there were no scratches. Furthermore, as a result of infiltrating IPA into Bencot and conducting a rubbing resistance test under the same conditions, it was confirmed by visual inspection and optical microscope observation that there were no scratches.

Claims (13)

The repeating unit structure is essentially composed of only the repeating unit structure represented by the following formula (1), has at least one triazine ring terminal, and at least a part of the triazine ring terminal is represented by the following formula (15). A hyperbranched polymer type triazine ring-containing polymer, which is sealed with the indicated fluorine atom-containing arylamino group.

{In the formula, R and R'represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group independently of each other.
Ar represents at least one selected from the group represented by the formulas (2) to (13).

[In the formula, R ^{1 to} R ⁹² are independent of each other and may have a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, a branched structure having 1 to 10 carbon atoms, or an alkyl group having 1 carbon atom. Represents an alkoxy group which may have a branched structure of 10 to 10.
R ⁹³ and R ⁹⁴ represent an alkyl group which may have a hydrogen atom or a branched structure having 1 to 10 carbon atoms.
W ¹ and W ² are independent of each other and have a single bond, CR ⁹⁵ R ⁹⁶ (R ⁹⁵ and R ⁹⁶ may have a hydrogen atom or a branched structure having 1 to 10 carbon atoms independently of each other. Represents an alkyl group (where they may form a ring together), C = O, O, S, SO, SO ₂ , or NR ⁹⁷ (where R ⁹⁷ is a hydrogen atom or Represents an alkyl group that may have a branched structure having 1 to 10 carbon atoms).
X ¹ and X ² are independent of each other and may have a single bond, a branched structure having 1 to 10 carbon atoms, or an alkylene group of the formula (14).

(In the formula, R ^{98 to} R ¹⁰¹ are independent of each other and may have a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, a branched structure having 1 to 10 carbon atoms, or an alkyl group having 1 carbon atom. Represents an alkoxy group which may have a branched structure of 10 to 10.
Y ¹ and Y ² represent an alkylene group which may have a single bond or a branched structure having 1 to 10 carbon atoms independently of each other. ) Represents a group. ] }

(In the formula, R ¹⁰² represents a fluorine atom or a fluoroalkyl group having 1 to 10 carbon atoms.) The first aspect of claim 1, which is a reaction product of a compound represented by the following formula (A), a compound represented by the following formula (B), and a terminal encapsulant containing a compound represented by the following formula (C). Triazine ring-containing polymer.

(In the formula, X represents halogen atoms independently of each other, R, R', Ar, and R. ¹⁰² Represents the same meaning as described above. ) The triazine ring-containing polymer according to claim 1 or 2, wherein R ^{1 to} R ⁹² and R ^{98 to} R ¹⁰¹ are hydrogen atoms. The triazine ring-containing polymer according to any one of claims 1 to 3 , wherein the fluorine atom-containing arylamino group is represented by the formula (16).

(In the formula, R ¹⁰² has the same meaning as described above.) The triazine ring-containing polymer according to any one of claims 1 to 4, wherein R ¹⁰² is a perfluoroalkyl group having 1 to 10 carbon atoms. The triazine ring-containing polymer according to any one of claims 1 to 5, wherein Ar is represented by the formula (17).

A film-forming composition containing the triazine ring-containing polymer according to any one of claims 1 to 6 and an organic solvent. The film-forming composition according to claim 7, wherein the organic solvent is at least one selected from a glycol ester solvent, a ketone solvent, and an ester solvent. The film-forming composition according to claim 7 or 8, further comprising a cross-linking agent. The film-forming composition according to claim 9, wherein the cross-linking agent is a polyfunctional (meth) acrylic compound. A thin film obtained from the film-forming composition according to any one of claims 7 to 10. An electronic device comprising a base material and the thin film according to claim 11 formed on the base material. An optical member including a base material and the thin film according to claim 11 formed on the base material.

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